Solar modulation of cosmogenic nuclide production over the last millennium: comparison between C and Be records

For about the last 30 years it has been recognized that the high frequency component of the tree rings ¹⁴C/¹²C record is dominated by the modulation of the cosmic ray flux by the solar wind. In particular, it has been demonstrated that the three most recent periods of low sunspot occurrence were characterized by high values of atmospheric ¹⁴C/¹²C. During the last millennium other periods of high ¹⁴C/¹²C values were observed but their solar origin is still debatable. In the present work we compare these fluctuations with an independent record of cosmogenic ¹⁰Be measured in ice from the South Pole to check the solar origin of the observed ¹⁴C/¹²C variations. In order to compare quantitatively the results obtained on ¹⁰Be and ¹⁴C, it is necessary to take into account the different behaviour of these two cosmogenic isotopes, and especially the damping effect of the carbon cycle in the case of ¹⁴C. As an input to a 12-box numerical model we used the relative fluctuations of the ¹⁰Be concentrations record measured in South Pole ice and converted it into a synthetic ¹⁴C record. We took into account the fact that ¹⁰Be modulation is enhanced in polar regions due to the orientation of the geomagnetic field. As expected, the fluctuations of the modelled ¹⁴C record are much smaller (a factor of 20) than those observed for the raw ¹⁰Be record. In addition, the variations are smoother and shifted in time by a few decades. The ¹⁰Be-based ¹⁴C variations closely resemble the ¹⁴C measurements obtained on tree rings (R = 0.81). In particular, it is easy to identify periods of maximal ¹⁴C/¹²C which correspond to solar activity minima centred at about 1060, 1320 (Wolf), 1500 (Spörer), 1690 (Maunder) and 1820 (Dalton) yr A.D. Cross-correlation calculations suggest that there is no significant lag between the ¹⁰Be-based ¹⁴C and the tree-ring ¹⁴C records. Our study strongly suggests the dominance of the solar modulation on the cosmonuclide production variations during the last millennium.     

The identifiability of parameters in a water quality model of the Biebrza River, Poland

The identifiability of model parameters of a steady state water quality model of the Biebrza River and the resulting variation in model results was examined by applying the Monte Carlo method which combines calibration, identifiability analysis, uncertainty analysis, and sensitivity analysis. The water quality model simulates the steady state concentration profiles of chloride, phosphate, ammonium, and nitrate as a function of distance along a river. The water quality model with the best combination of parameter values simulates the observed concentrations very well. However, the range of possible modelled concentrations obtained for other more or less equally eligible combinations of parameter values is rather wide. This range in model outcomes reflects possible errors in the model parameters. Discrepancies between the range in model outcomes and the validation data set are only caused by errors in model structure, or (measurement) errors in boundary conditions or input variables. In this sense the validation procedure is a test of model capability, where the effects of calibration errors are filtered out. It is concluded that, despite some slight deviations between model outcome and observations, the model is successful in simulating the spatial pattern of nutrient concentrations in the Biebrza River.     

Tectonic evolution of the Lachlan Fold Belt, southeastern Australia: constraints from coupled numerical models of crustal deformation and surface erosion driven by subduction of the underlying mantle

We have used a coupled thermo-mechanical finite-element (FE) model of crustal deformation driven by mantle/oceanic subduction to demonstrate that the tectonic evolution of the Lachlan Fold Belt (LFB) during the Mid-Palaeozoic (Late Ordovician to Early Carboniferous) can be linked to continuous subduction along a single subduction zone. This contrasts with most models proposed to date which assume that separate subduction zones were active beneath the western, central and eastern sections of the Lachlan Orogen. We demonstrate how the existing data on the structural, volcanic and erosional evolution of the Lachlan Fold Belt can be accounted for by our model. We focus particularly on the timing of fault movement in the various sectors of the orogen. We demonstrate that the presence of the weak basal decollement on which most of the Lachlan Fold Belt is constructed effectively decouples crustal structures from those in the underlying mantle. The patterns of faulting in the upper crust appears therefore to be controlled by lateral strength contrasts inherited from previous orogenic events rather than the location of one or several subduction zones. The model also predicts that the uplift and deep exhumation of the Wagga-Omeo Metamorphic Belt (WOMB) is associated with the advection of this terrane above the subduction point and is the only tectonic event that gives us direct constraints on the location of the subduction zone. We also discuss the implications of our model for the nature of the basement underlying the present-day orogen.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Variations of U and Sr isotope ratios in Alsace and Luxembourg rain waters: origin and hydrogeochemical implications

Major and trace element concentrations, as well as Sr and U isotope ratios, were measured in rainwater samples collected in three different locations in Alsace (East of France) and Luxembourg: a mid-altitude mountain site (Aubure Environment HydroGeochemical Observatory), an urban site (Strasbourg) and a peri-urban site located in an area of well developed industrial activity (Esch-sur-Alzette in Luxembourg). Results highlight the quite high spatial and temporal variability of the chemical and isotopic characteristics of rainwater at the regional scale. They also suggest a quite systematic contribution of a local component in the chemical composition of rainwater. In urban and peri-urban sites, the local component is certainly linked to human activities, as it is well illustrated in this study with the Esch-sur-Alzette samples. On the other hand, for the Aubure site, i.e. a small forested watershed of mid-altitude mountain, data presented in this study demonstrate the influence of the vegetation on the chemical composition of rainwater for alkali and calc-alkali elements, as well as for the Sr isotope ratios. Such a result questions the reliability of the method classically used to estimate the rainwater contribution on the river chemical budget. In addition, data of the present study confirm the very low content of uranium in rainwater and demonstrate, especially through the U isotope analysis of Aubure rainwater, the negligible effect of rainwater on U budget of river waters. This work thus outlines the property of U to be a geochemical tracer specific of weathering fluxes carried by rivers. To cite this article: F. Chabaux et al., C. R. Geoscience 337 (2005).